Reactive dyes of the 1, 4-diamino-anthraquinone-2-sulfonic acid series



United States Patent 3,296,284 REACTIVE DYES OF THE 1,4-DIAMINO-ANTHRA-QUINONE-Z-SULFONIC ACID SERIES Wolfgang Schoenauer, Riehen, Basel-Stadt,Switzerland, 'assignor t0 Sandoz Ltd., also known as Sandoz AG,

Basel, Switzerland No Drawing. Filed Oct. 14, 1964, Ser. No. 403,937Claims priority, application Switzerland, Sept. 12, 1960, 10,299/60 4Claims. (Cl. 260-372) The present application is a continuation-in-partof my application &r. No. 135,785, filed September 5, 1961, nowabandoned.

It relates to water-soluble reactive dyes of the anthraquinone serieswhich correspond to the formula II I {A SOQH I! l 0 NH B OH -N'H-OOO=CH:

hat (I) wherein .hal is chlorine or bromine,

the ring A is selected from the group consisting of unsubstitutedphenylene, sulfophenylene, bromophenylene, chlorophenylene,dichlorophenylene and fluorophenylene,

and the nucleus B bears one to three substituen-ts selected from thegroup consisting of lower alkyl and lower alkoxy groups.

In the ring A the sulfonic acid group may be attached to any one of thepositions 5, 6, 7 and 8, whereas the halogen atom or atoms may beattached only to one of the positions 6 and 7.

The alkyl and alkoxy substituents of the nucleus B contain 1 to 5 carbonatoms (methyl, ethyl, n-propyl, isopropyl, n-butyl, tert.-butyl, n-amyl,isoamyl, tert.-amyl, methoxy, ethoxy, n-propoxy, n-butoxy andn-arnyloxy).

A group of particularly valuable dyes comprises those of the formulaCHze-NH-C 0-0 0 H2 wherein X is methyl or ethyl,

Y is methoxy or ethoxy,

m is one of the integers l, 2, 3 and 4, and

n is one of the integers 1 and 2,

the sum m+n is at least 3 and at most 5.

3,296,284 Patented Jan. 3, 1967 ICC i The process for their productionconsists in reacting an anthraquinone dye of the formula 8 sour ii n,

- (III) N-methylol-arnides conforming to the invention; they areprepared in known manner by reacting the a-halOgenoacrylic acid amideswith paraformaldehyde.

The u-bromo or a-chloro-acrylic acid-Nthloro-methylamide or-N-bromomethylamide"are produced by reacting an halogerroacrylicacidamide'anda symmetrical dihalogenodi-methyl'ether e.g. inconcentratedsulfuric acid and are employed immediately in form of their sulfuricacid solution. ,7 [W1 V V The reaction is carried outin sulfuric acidsolution, e.g. in 80% to 100% sulfuric acid, at temperatures of 0 toabout 60 C., especially 0 to30" C.,' over a'period of several 'hours'. I

The dyes are isolated e.g. by pourin'g the sulfuric acid solution ontoice, filtering off the precipitate, washing with a solution of sodium orpotassium chloride until the filtrate is neutral and drying. V, v

The dyes so obtained are suitable for-dyeing leather; for dyeing,padding and printing fibers of animal origin, e.g. wool and silk;synthetic polyamide fibers, e.g. nylon; cellulosic fibers, e.g. cottonand linen; fibers of regenerated cellulose, e.g. viscose filament yarn,viscose staple fiber and cuprammonium rayon; and mixtures and articlesof these fibers. The optimum conditions of application vary with thetype of fiber and the dyes used.

Animal and synthetic polyamide fibers are dyed, printed medium, e.g. inpresence of acetic, formic or sulfuric acid, ammonium sulfate, sodiummetaphosphate etc.

They can also be applied from acetic acid to neutral medium in presenceof levelling agents, e.g. polyoxethylated fatty amines or mixtures ofthese and alkylpolyglycol ethers, and the bath adjusted to a neutral orweakly alkaline reaction at the end of dyeing by the addition of smallamounts of an agent of alkaline reaction, e.g. ammonia, sodiumbicarbonate, sodium carbonate etc. or a compound which reacts alkalineon heating, e.g. hexamethylene tetramine or urea. Thegoods are thenrinsed well and if necessary soured With a little acetic acid. Thedyeings and prints in general possess good fastness to light, washing,milling, water, perspiration, crocking and dry cleaning.

The dyeing, padding and printing or fixing of the dyes on cellulosicfibers is carried out advantageously in alkaline medium, e.g. inpresence of' sodium bicarbonate, sodium-carbonate, sodium hydroxidesolution, potassium hydroxyde solution, sodium metasilicate, sodiumborate, trisodium phosphate, ammonia. To prevent reduction effects indyeing, padding or printing, it is often of advantage to add a mildoxidizing agent, e.g. sodium 1- nitrobenzene-3-sulfonate. As a rule thefixation of the dyes on cellulose fibersalso is carried out withheating.

The dyeings and prints on cellulosic fibers possess excellent wetfastness properties, due to the formation of a chemical linkage betweenthe dye molecule and the cellulose molecule. Often the entire amount ofdye applied does not take part in the reaction with the fiber; thisunreacted dye is removed from the fiber by suitable treatment such asrinsing and/ or soaping, if necessary at high temperatures, for whichpurpose synthetic detergents can be used, e.g. alkylarylsulfonates,sodium lauryl sulfate, sodium" laurylpolyglycol ether sulfate,alkylpolyglycol ethers and monoand dialkyl-phenylpolyglycol ethers,which may be carboxymethylated if desired. The dyeings and prints on thecellulosic fibers possess good fastness to light, washing, water,perspiration, crocking and dry cleaning. I

In comparison with the next'comparable dyes of the French patent No.1,222,194 which carry a group CH NHCOCH Cl, eLg. the dye of Example 6,the dyes of the present invention are much more reactive on cellulosicfibers. I,

In the following examples the parts and percentages are by weight andthe temperatures in degrees Centigrade.

Example 1 10.5 parts of a-chloroacrylic acid amide are dissolved in 75parts of concentrated 99-l00% sulfuric acid at -15. The solution iscooled to 05 and 6 parts of dichlorodimethyl ether are added dropwise in1 hour. After stirring for a further hour at 0-5", the temperature isincreased to' l0 l5 and stirring continued for 16 hours at thistemperature.

6.9 parts of the sodium saltof 1-amino-4-(2',4',6'-trimethylphenylamino)anthraquinone-2-sulfonic acid are dissolved in 140 parts of 96% sulfuricacid. 16.5 parts of the sulfuric acid solution of the condensationproduct of a-chloroaerylic acid amide and dichlorodimethyl etherdescribed above are added dropwise at 0-10 in about minutes. The mass isstirredfor 24 hours at 10-15 and the solution then run onto 400 parts ofice. The precipitate formed is filtered off and washed with a dilutecommon salt solution until neutral. The filter cake is suspended inwater and the pH adjusted to 7 with dilute sodium hydroxide solution.Then the dye is precipitated with common salt, filtered, washed with a'dilute common salt solution and dried. It dyes wool blue from a weaklyacid bath, the dyeings being vvery fast to inilling.

2 parts of this dye, 0.8 part of an .oxyethylated fatty amine and 0.5part of an oleylpolyglycol ether are dissolved in 5000 parts of water,and 2 parts of glacial acetic acid are added to the solution. Thisdyebath is heated to 40-50"v and at this temperature 100 parts of woolare en tered. The bath is brought to the .boil in 30 minutes andmaintained at the boil for 45 minutes, after which the wool is, rinsedand dried. A level blue dyeing very fast to light and wet treatments isobtained. If the dyebath is neutralised with ammonia on completion. ofdyeing and the goods treated in it for minutes at 90, 21 dyeing ofslightly better wet fastness is obtained. However the same result can beobtained by aftertreating the dyed goods for 20-30 minutes in a freshbath of 5000 parts of Water and 3 parts of hexamethylene tetramine at9095.

2 parts of dye are dissolved in 3000 parts of soft water at about 30";100 parts of mercerized cotton sateen are entered in this solution whichis brought to 90 in the course of about 30 minutes. 180 parts ofcalcined sodium sulfate are added in 4 portions at 30, 50, 70 and 85 and45 parts of calcined sodium carbonate at 90. Then the dyebath ismaintained for 1 hour at 90-95. After removal of the dyed cotton the dyecontent of the liquor is determined by colorimetry.

In order to remove the non-fixed portion of dye, the dyed cotton iswashed for 20 minutes at the boil in 3000 parts of water containing 1.5parts of a carboxymethylated alkylpolyglycol ether and 1.5 parts ofcalcined sodium carbonate. The washed dyeing is removed and the amountof dye in the solution is determined by colorimetry.

The fixation yield amounts to 21%. The blue dyeing is fast to light,washing, water, perspiration, crocking and dry cleaning.

The same dyeing procedure carried out with the dye of Example 6 of theFrench Patent 1,222,194 which bears a chloroacetylaminomethyl groupinstead of the a-chloroacryloylaminomethyl group leads to a fixationyield of only 10.7%.

Example 2 a 6.7 parts of sodiuml-amino-4-(2',6'-dimethylphenylamino)-anthraquinone-Z-sulfonate aredissolved in parts of 96% sulfuric acid at 10-20. To this solution areadded in about 15 minutes 2.5 parts of a-chloro-. acrylicacid-N-methylolamide and the mass is then stirred for 24 'hours at l020.The solution is poured onto 400 parts of ice and isolated as describedin Example 1. The thus produced dye' is very similar to that of Example1 and dyes wool and cotton in blue shades fast to light and to wettreatments.

By placing the 2.5 parts of a-chloroacrylic acid-N- methylolamide by 3.3parts of a-bromoacrylic acid-N- methylolamide, a similar dye isobtained.

Example 3 6.7 parts of sodium1-amino-4-(4'-methoxyphenylamino)-anthraquinone-2-sulfonate aredissolved at 5-10" in parts of 95% sulfuric acid. After cooling to 0,16.5 parts of the sulfuric acid solution of the condensation product ofa-chloroacrylic acid amide and dichlorodimethyl ether described inExample 1 are added dropwise at 0-5 in about 15 minutes. The temperatureis maintainedv at 0 for two hours and subsequently the mass is stirredfor 20 hours at 10-15". The dye is isolated in the manner described inExample 1; it dyes wool in blue shades fast to light and to wetagencies.

By replacing the condensation product of a-ChlOI'O- acrylic acid amidewith dichlorodimethyl ether by that of a-bromoacrylic acid amide withdichlorodimethyl ether a very similar dye is produced.

The following table contains further dyes obtained according to theparticulars of Examples 1 to 3. They correspond to the formula NH: sourii I IH 2,1324

CHNH-COC=OH,

" al (iv and are characterized by the phenylene radical A (column (1))by the phenyl radical of the dyeings or prints on wool or on cotton(column (IV)). The radical is attached to the nucleus B in a positionvicinal to an alkyl or alkoxy group.

TABLE Exaigple (I) (II) (III) (IV) 4 Phenylene 4-n1ethy1phenyl Greenishblue r d 2,4-dimethylpheuyl D0, do V D0. 2,4,6-t1'1methylpheny1 Blue.

go Do,

Reddish blue.

echlorophenyleneuu .d0 e. 6,7-dichl0rophenylenei d0 Do.

4-ethylphenyl Greenish blue. 4-isopropylphenyl Do. 2,5-dimethylphcnylDo. 4-tert.-butylphenyl u Do. 4-tert.-amylpl1enyl Do.

i ,do D o. 2-methyl-4-n-butyl-phenyl D 0.

do D o.

. o Blue.

2,4-dimethyl-6 ethylplienyl Reddish blue. 4-ethoxypl1enyl Greenish blue.4-n-p1'0p0xypheny1 Do. 2-metl10xy-5-methyl-phenyl Blue.2,5-dimeth0xyphenyl Do. 2-meth0xypheuyl Do 2,6-dimethyl-4-n-butylphenyL.Reddish blue.-

do Blue.

4-n-amyloxypheny Greenish blue; 4-isoamylphenyl- Do. 4-n-butylphenyl D0.2,5'-diethoxyphenyl Blue. 4-n-propylphenyl Greeuish blue.ZQGglimethylphenyl IIgteddish blue.

n... o lue.

fi-fluorophenylene. D 4, G-brornophenyleue. 43 7-chlorophenylene Reddishb 44 6,7-dichlorophenylene. do A Blue. 45 Phegylene Zi-etgoxyrgethglphenyl Greiish blue. 4 o -nutoxyp eny 0. 47 g-gulfophenylene,2,4,6-ti'imethylphenyl Blue.

Phgny1e1 e 2,4-cliethoxypheuyl Greenish blue.

2'-methyl4'-methoxypheuyl Do. 2-methy1-5-methoxyphenyl Do.

Formulae of representative dyes of the foregoing exof the formula amplesare as follows: 0 NHI II I Example I A SOQH 0 H2 45 A H I s CH3 (lJHNH-COO=CH2 CHPNHA] 50 1 NH OH: hal

Example 2 wherein P hal is a halogen atom selected from the groupconsisting of chlorine and bromine, 303E the ring A is selected from thegroup consisting of unsubstituted phenylene, sulfophenylene,fluorophenyl- E CHFNH CO O=CH ene, brornophenylene, chlorophenylene and6,7-di- 1 chlorophenylene, the single halogen atom being at- O NH tachedto one of the positions 6 and 7, and sulfo j being attached to one ofthe positions 5, 6, 7 and 8, and the nucleus B bears one to threesubstituents se- Example 3 lected from the group consisting of loweralkyl and NH lower alkoxy, 2 and the group -SO3H CH NH-O 0-0=0H, (IJHNHCOO= H: hai liege-CH3 being bound in ortho-position to a substituentof the Having thus disclosed the invention, what I claim is: nucleus B.

2. An anthraquinone dye of the formula wherein X is a member selectedfrom the group consisting of methyl and ethyl,

Y is a member selected from the group consisting of 15 (III) NH:

II 1 0 NH- on 4. The anthraquinone dye of the formula II I SOaH

References Cited by the Examiner FOREIGN PATENTS 1,200,241 6/1959France. 1,222,194 1/1960 France. 1,238,515 7/1960 France.

830,876 3/1960 Great Britain.

LORRAINE A. WEINBERGER, Primary Examiner.

R. K. JACKSON, H. C. WEGNER, Assistant Examiners.

1. AN ANTHRAQUINONE DYE OF THE FORMULA